Handbook for Field Hydrological

Measurements
Department of Earth Sciences – Hydrology and
Geo-environmental Sciences

Boris M. van Breukelen, Michel M.A. Groen, Koos Groen, Ko

van Huisteden, Richard A.M. de Jeu, Vincent E.A. Post, Jaap
Schellekens and Maarten J. Waterloo

Amsterdam, April 2014

2
 Part VIII

Hydrochemistry

3
Chapter 11

Hydrochemical field investigation

procedures

11.1 Background
Water is a transport medium for all kind of substances, including nutrients, pollu-
tants, gases and sediment. The chemical composition of rain water infiltrating in
soil or rock is changed by many processes, including evaporation, dissolution of
minerals, redox reactions, mixing processes (e.g. fresh water and sea water) and
biological and anthropogenic processes (e.g. pollution, agriculture). As dissolution
of minerals is a generally a very slow process, the residence time of the water in
the medium is a factor of importance. All these processes lead to a certain enrich-
ments or depletions of ions in river and ground water. Studying the hydrochemistry
of precipitation, river and ground water in an area may therefore give clues to the
importance of the various processes determining the water quality. Studying the
chemistry of water is therefore often considered a very useful aid to improve our
understanding of the hydrological processes acting in an area.
In this chapter we shall describe the procedures for obtaining reliable analyti-
cal results from collected water samples. This includes planning, laboratory sample
preparations and descriptions of field measurements of certain parameters that are
sensitive to changes between sampling and analysis. Following these procedures
increases the quality of the data that you will collect and ensures a successful hy-
drochemical field work.

11.2 Pre-sampling procedures and planning

It is good practice to reflect on the following questions before you are going out to
the field to collect water samples for hydrochemical analysis:

• What is the research question, can it be addressed through sampling of wa-

ter?

137
 • What are the minimum and optimum sets of parameters that you should in-
clude in the sample analyses? Remember that sample analysis is a time con-
suming and costly activity (at least 50 euro per standard sample analysis).
• What is the optimum number of samples to be collected in time and space to
solve your research question?
Part of the planning of your research programme is to make sure that your
samples are analysed in a timely fashion. This is also because the chemical com-
position of your sample is likely to change to a certain extent during storage (e.g.
−
pH, HCO3 , etc.). When you are collecting samples for fieldwork or laboratory
studies that need to be analysed certain procedures need always to be followed.
If samples are to be analysed in a commercial laboratory, you need to contact
them about sample procedures and delivery and the timing of the analysis. If the
analysis is done at the water chemistry laboratory of the Institute of Earth Sciences
at the VU, you should do the following:
a. Make an agreement about your planning with the laboratory analyst (Mr. John
Visser) and inform the laboratory manager (Dr. Boris van Breukelen) about the
number of samples, the desired analysis and the time frame for your sample
analysis.
b. Make the necessary preparations for avoiding sample contamination and for
the conservation of your sample between the time of collection and the actual
analysis. To avoid changes in your sample chemistry during storage, acidified
sample bottles are used for the analysis of cations (ask the lab analyst for full
details). The procedure for preparing your sample bottles is in short:
• Rinse all sample bottles/caps in advance with a concentrated HNO3solution,
then flush them several (5) times with demineralised water and finally rinse
with distilled water.
• Dry the cleaned bottles/caps
• For sample conservation add 0.7 ml concentrated HNO3(65% suprapur)
per 100 ml sample volume to your cleaned bottles. If you use 50 ml sam-
ple bottles, add 0.4 ml of HNO3.
• Always mark the acidified bottle and its cap with a large red dot to indicate
that it contains acid!
• In consultation with the lab analyst, stickers can be made that list the lab-
oratory numbers.
• Download the excel template sheet from the Laboratory for Water Chem-
istry link at http://ecohydro.falw.vu.nl (get user name and password from
Boris van Breukelen or John Visser) and study it so that you know what
to measure and note down in the field. You are required to upload this
file containing the metadata for your sample before your samples can be
analysed.

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 11.2.1 Required material
Make sure that you have the following packed before you leave for the field.

I. Sufficient clean sample bottles, as well as acidified sample bottles. For the
laboratory analysis of a single sample for main cations and anions you will
need:

• 1 clean and acidified 50 ml bottle for cation analysis

• 1 clean 10 ml bottle for anion analysis
• 1 clean 50 ml bottle for laboratory alkalinity determination and labora-
tory pH and EC measurements (optional)
• 1 clean 30 ml amber-coloured glass bottle for δ18 O and δ2 H analysis
(optional).

II. At least one 50 ml syringe for filtering of sample water and sufficient 0.45
µm pore size filters. We use single-use Millipore nitrate-cellulose or nitrate-
acetate filters for this purpose. Note: depending on the suspended matter
concentration in your sample you may need up to 10 filters to filter 50 ml of
sample water. However, usually one or two filters per sample is sufficient.

III. Electrical conductivity and temperature meter

IV. pH meter and calibration buffer fluids. Do not use pH strips as these are not
very accurate.

V. Dissolved oxygen (O2) meter (optional).

VI. Flow through cell or container to place your field electrodes (optional, see
Figure 11.1).
− −
VII. A titration kit for field alkalinity (HCO3 ) determination (and optionally Cl ,
−
Ca2+, Ca2++ Mg2+ ). You should always determine HCO3 while sampling
because the concentration will change rapidly in your sample bottle.

VIII. Test strips for nitrate (optional).

IX. A pump and sufficiently long tubing for groundwater sampling in piezome-
ters.

X. A field book, pencil, yellow tape and markers to code sample bottles.

XI. A cool-box to store your water samples cool during their transport to the
laboratory refrigerator (optional).

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Figure 11.1: PVC–perspex flow through cell with electrodes to measure the pH
and EC of water pumped from a well and passing through the cell without being
exposed to air.

11.3 Field sample collection procedures

11.3.1 Methods to obtain water samples
In a hydrological study you may want to analyse different types of water, including
precipitation, river water and groundwater. The procedures differ slightly and will
be discussed below.

Sampling of water from collectors

Rainfall, throughfall, litter percolate or transpired water can be collected in clean
rain gauges or sample bags made from chemically inert material. The collectors
have to be rinsed with a diluted HNO3 solution to remove ions sorbed to the col-
lector material, followed by thorough rinsing with distilled water (6 times). After
a rainfall event the water can simply be sampled according to the normal sample
procedures (acidification, filtering) described above. Be sure to sample the water
as soon as possible after the rainfall event to avoid changes due to storage and
evaporation in the collector.

River and lake water sampling procedure

Sampling of well-mixed turbulent surface water is normally rather straightforward.
You must take the surface water sample ideally just below the water surface away

140
Figure 11.2: Soil moisture suction cup used for the extraction of moisture from the
unsaturated zone.

from the river banks, preferably in the river section where flow is most turbulent to
ensure proper mixing of the water. Note that the hydrochemistry of water close to
the river banks or at the bottom or surface of the river may differ from the overall
river water chemistry due to poor mixing.
Sampling in less turbulent water, such as lakes, pools or stagnant rivers, is much
more cumbersome as stratification may have developed. This often means that a
layer of warm, oxygen-rich water at the surface may be floating on top of cooler
bottom water, which may even be anoxic if the lake is deep enough. In such an
environment it may not be possible to take a single sample that is representative for
the water body and several samples then have to be collected from different depths
to get an idea of the hydrochemistry. Such stratification can even be observed in
small, shallow lakes with depths of less than 50 cm (e.g. Lagoa da Jincosa in
Portugal).

Phreatic zone soil moisture sampling procedure

Soil moisture sampling from the unsaturated zone can be done with a porous cup
sampler (also called suction lysimeter). This is a PVC tube with a porous cup glued
to one of the ends (see Figure 11.2). A stopper with two smaller diameter tubes is
inserted into the other end of the tube. These tubes are used to evacuate the sampler
and to collect water from the sampler.
When the sampler is installed into moist soil (pF<2.7), the under-pressure in
the sampler will create flow of soil moisture through the porous ceramic cup into
the sampler. The water can be sampled by putting air pressure on the short tube,
causing water to flow out of the longer tube extending from the sampler.
The porous cup can be made of ceramic, teflon or sintered metal. The first two
materials are less suitable because of hydrophobicity (teflon) and high exchange
capacities and oxidation (metal) influencing the hydrochemistry. Ceramics (porce-
lain) is therefore often the best option due to its inertness and toughness.
Alternatively, unsaturated soil may be sampled for pore water extraction. The
moisture may be extracted by centrifugal action in the laboratory.
The use of porous cups allows for the development of hydrochemical time
series for soil water, whereas this is not possible using the destructive soil sampling

141
method.

Ground water sampling

Various methods exist for groundwater sampling. Groundwater bailers (Dutch:
water happer) are very useful to take samples from large-diameter open wells,
which are abundantly present in the Portugal field work areas (Portuguese name:
nora or poço). The closed bailer is slowly lowered below the water level to the
desired sampling depth and opens when rapidly pulled upwards. Note that the
water composition in open wells may not truly reflect the aquifer hydrochemistry
as the well also collects rain water (dilution) and is affected by evaporation and
oxidation.
Before sampling groundwater from a piezometer, always remove at least three
times the volume V (in l) of standing water (V = 3πr2l), where r is the diameter
of the piezometer and l the length of the piezometer filled with water. This ensures
that you obtain a water sample representative of the aquifer. The standing water
in the piezometer may have a different chemical composition than the aquifer be-
cause evaporation and oxidation may have occurred and stratification may have
developed.
In Portugal, some deep wells (called furos) may have taps installed. Springs
(called fonte, Figure 11.3) may have been captured and and have taps installed that
drain water from a storage reservoir. In this case, let the water run for a while
before you start sampling.
Several types of pumps are available to extract water from wells for ground-
water sampling. The most frequently used pumps are peristaltic pumps (small
volumes, for instance for sampling through minifilters), submerged pumps (large
volumes) and inertial pumps. Examples of such pumps are shown in Figure 11.4.
Avoid the use of a vacuum pump to extract water from a piezometer, as its use re-
sults in strong degassing, associated pH increases and mineral precipitation during
sampling. A peristaltic pump creates much smaller suction forces and can safely
be used if the water table is less than a few meters below surface. It is better to
use a submersible Grundfos pump or a mechanical inertial pump when the water
table is at a depth of more than 5 m. These pumps push the water up and cause no
degassing at all. Small-diameter (2.5–10 cm) groundwater piezometers can easily
be sampled manually with a simple inertial pump consisting of a couple of me-
ters tubing with a ball-valve attached at the end. By moving the tubing rapidly up
and down, it fills with water each time you move it downwards and the ball-valve
ensures that water cannot flow out of the tube once it has entered during the down-
ward movement (a mechanical version of the system is shown in Figure 11.4).
If there are no other means of sampling your aquifer water, you can install
your own observation piezometer (see Chapter 8 on how to drill holes and install
wells). Please take a moment to reflect on the diameter of the piezometer. Larger
diameter (5 cm) piezometers provide access to submersible pumps (see later) or
the EM-39 borehole sounding device (Chapter 9). At least two small diameter (2.5

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 Figure 11.3: Fonte 006 in the Vagos research are near Aveiro.

Figure 11.4: Overview of pumps available to collect groundwater: Barnant Com-

pany E/S portable water sampler with a peristaltic pump (left), Grundfos sub-
mersible pump (center) and Waterra inertial pumps with ball valves (right).

143
Figure 11.5: A minifilter (right) consists of plastic cylinder (part of syringe) filled
with filter wool. One end is attached to the sampling tube and the broad end is
open. This filter is attached to the exterior of a piezometer, covered with filter cloth
and taped in place on both sides at the desired depth (right).

cm) piezometers fit in one manually drilled borehole (diameter 10 cm). Usually,
you will have to delay sampling for at least a week after installation, but preferably
for several months, before reliable groundwater samples can be obtained. This
stabilisation period is required because the local aquifer hydrochemistry has been
disturbed by the drilling. If you can not wait that long, be sure to pump as much as
water until the groundwater becomes clear.
If you want to obtain information on the variation in hydrochemistry with
depth, we advise you to attach minifilters at the outside of a piezometer. These
can be made easily by taping a few cm length of filter cloth to a 2–3 mm diame-
ter tubing (or syringe casing) that is taped to the outside of the piezometer at the
desired depth (Figure 11.5). Do not forget to clearly label the tubing at the sur-
face: indicate the number of the miniscreen and its depth. Make the tube of each
shallower minifilter around 5 cm longer than the one on a deeper level, so that you
always know the depth order of the miniscreens in case the labels have become
unreadable after time.

On-site hydrochemical analysis

Because several key parameters may change rapidly during storage of a water
sample, acidity (pH), temperature, electrical conductivity (EC), alkalinity (and
optionally oxygen concentration) have to be determined during sampling. For-
tunately, these parameters are easily determined with electrodes (except for alka-
linity). Monitoring these parameters during sampling (via flow through cells) also
enables deciding when the ground water well has been sufficiently flushed to begin
sampling. Always calibrate the electrodes before use (check the manuals for cali-
bration procedures). pH meters show considerable drift and must be calibrated at
least once a day, but preferably before each samples is taken. EC and temperature
meters are very stable and only need to be calibrated before you leave for field

144
work. Only alkalinity must be determined, preferably in duplicate, via titration by
means of a field digital titrator (Hach, Germany). You can check nitrate/nitrite
concentrations using nitrate test strips (Merck, USA), especially if nitrate analysis
is not possible the next day.
If a project does not allow time for laboratory analysis, or if samples cannot be
shipped to a laboratory, some parameters may be determined via titrations as soon
as possible after sampling and preferably on the same day(!) by means of a field
digital titrator set (Hach, Germany). These include Ca2+, hardness (Ca2++ Mg2+)
and Cl−.

Conservation of water samples

Water samples must always be conserved in some way, because otherwise the con-
centrations of the hydrochemical parameters may change during storage until anal-
ysis. If a (potentially anaerobic) groundwater sample is brought to the surface the
following physical-chemical conditions will be altered with the following effects:

1. A decrease in pressure causing degassing (of CO2) and thereby inducing a

pH increase and potential precipitation of minerals like calcite.

2. Oxidation of ammonium (to nitrate by microbial oxidation) and reduced met-

als (lowering their concentration by precipitation to mineral phases), while
alkalinity becomes lowered if reduced ferrous iron (Fe2+) oxidises.

3. A higher temperature enhances microbial activity, induces precipitation of

carbonate minerals, and may lead to evaporation and thereby higher concen-
trations of all solutes.

4. Light may result in growth of algae and corresponding hydrochemical changes.

Water samples must therefore always be stored under preferably cool condi-
tions, out of direct sunlight, with the bottle filled completely and capped tightly to
avoid leakage.
In general two sample bottles are used, one for anion and one for cation anal-
ysis. The first 50 ml(or 10 ml) sample tube, for anion analysis, must be filtered
to make the sample optically clear. This allows good colorimetric analysis in the
laboratory. You need at least 50 ml, if this water is also used for laboratory EC and
pH measurements and, optionally, for laboratory alkalinity titration. The sample
bottle should first be flushed three times with sample water before the sample is
taken, filling up the bottle completely whenever possible.
The second 50 ml sample bottle, for analysis of cations, must also always be
filtered and acidified down to a pH < 2 (by adding concentrated HNO3 in a 1:100
dilution). Filtering and acidification prevents mineral precipitation and impedes
oxidation processes and bacterial activity, thereby conserving the sample. Filtering
is required before acidification because the strong acid will dissolve suspended
matter, resulting in increased concentrations.

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 Table 11.1: Water type codes for sample descriptions.
Water type Code
Soil core water CW
Groundwater observation well GWO
Groundwater abstraction well GWP
Groundwater infiltration well GWI
Laboratory experiment LAB
Litter leachate LL
Lake water LK
Precipitation (bulk) PB
Precipitation (wet only) PW
Sea water SEA
Soil moisture SM
Stem flow SF
Solid phase SP
Surface water (river, spring, etc.) SW
Throughfall TF

Always start with the anion analysis sample bottle and fill the acidified sample
bottle afterwards, because you may accidentally transfer some HNO3 to the non-
acidified bottles (contamination), increasing nitrate and lowering the pH. Use a
syringe and 0.45 µm filter for filtering. Use a fresh filter for each new sample.
When you need to refill the syringe with sample water, first detach the filter and
then pull out the plunger. If you pull out the plunger with the filter attached, the
vacuum created will tear the filter.

11.3.2 Water sample coding

Code water sample bottles with a waterproof marker on both bottle and cap. Give
each sample a short clear code that also identifies your initials/name, student group,
or study area and the water type. Note down all measured information at the sam-
pling location in a notebook and determine the coordinates with a GPS. For in-
stance, if your first sample is of river water, and your name is Jack Jones, then you
may want to call the sample JJ-SW1 (SW for surface water), whereas your second
sample would be JJ-SW2. A list of water types used by the Laboratory for Water
Analyses is given in Table 11.1.

146
11.4 Laboratory analysis
11.4.1 Sample metadata requirements
Before the samples can be analysed, the laboratory staff needs some details about
the samples for determining if dilution is needed, or if there are any other specifics
about the sample that require special treatment. It is to upload the sample data
before analysis can start. Details about the procedure can be found on the Water
Laboratory web page at http://ecohydro.falw.vu.nl.
Single samples can be entered in the laboratory database using a form, whereas
a template spreadsheet file is available for multiple samples. Be as complete in your
sample description as possible and do add remarks on sample colour, filtered/non-
filtered, acidified, specifics of sample site, discharge or volumes (mm) in case of
river water, rainfall, throughfall, litter percolate, etc. The required fields are: Sam-
ple code, Site or well ID, Filter no., Date, Time, Country code, UTM Zone, Lat-
itude, Longitude, Sample type, Discharge (or flux in case of rainfall, throughfall,
etc.), Upper filter level, Lower filter level, Topographic height, Remarks, Field pH,
Field EC, Field Temperature, Project name, Sub-project name/SAP number, Inves-
tigator name, Observer, Alkalinity, Field Cl, Field Ca, Field Mg, Field NO3 and
Dissolved O2.
In the laboratory you will receive stickers to place on your sample bottles and
you will have to assist the laboratory analyst with filling analysis vials, making
sample dilutions, and measuring the laboratory pH, EC and alkalinity.
All metadata and analytical results are stored in a database and can be retrieved
through the water laboratory web site at http://ecohydro.falw.vu.nl.

11.4.2 Analytical procedures

− − − 2− + 3−
Anions (Cl , NO3 , NO2 , SO4 ) and nutrients (NH4 , PO4 ) are analysed on a
Labmedics Aquakem 200 discrete analyser (DA; Figure 11.6). This instrument can
also be used to measure alkalinity via colorimetry. However, alkalinity is usually
measured via inflection point titration on a Radiometer Titralab TIM840 titration
workstation (automatic titrator; Figure 11.6). All DA methods are based on col-
orimetry, i.e., the adsorbance of a sample at a certain wave length (colour) after
addition of certain reagents is taken as measure of the concentration of a certain
chemical. Anions (+ Br) can also be determined via ion chromatography (IC; Fig-
ure 11.6) on a Dionex DX-120 IC equipped with IonPac AS14 column. Cations
(Ca, Mg, Na, K, Fe, Mn, Al and Si) are determined using the acidified samples
by means of a Varian 730-ES inductively coupled plasma-optical emission spec-
troscopy (ICP-OES, Figure 11.6). If you wish, ICP-OES can also simultaneously
measure a whole suite of spore elements and heavy metals (B, Ba, Be, Sr, Li, Mo,
As, Cd, Co, Cr, Cu, Ni, Pb, Se, Sb, V, Zn) together with total P and S. For some
projects you may be interested in measuring other parameters such as methane,
dissolved organic carbon (DOC), or H2S. Contact Boris van Breukelen for details

147
on sampling conservation and analysis.

11.5 Checking the accuracy of analytical results

Usually you analyse or obtain your analysis results in weight units like mg l−1 or
ppm. Note that mg l−1 equals ppm (part per million by weight of sample) for
dilute fresh waters (density = 1.0 g cm−3), while mg l−1 is slightly higher than
ppm for waters having a salinity of seawater (density = 1.023 g cm−3; 1 ppm =
1.023 mg l−1). To assure that errors were not made during lab analysis you can:
1. Calculate the electrical balance (EB, in %, see Equation 11.1 with concen-
tration units in meq l−1) of the water samples after having recalculated the
concentration units to meq l−1, together with
Σ Σ
cations + anions
EB = Σ Σ ∗ 100 (11.1)
cations − anions
2. the EC rule-of-thumb (Equation 11.2). Try to determine what went wrong if
errors are too large (> 5%). Probably some parameters must be re-analysed
once it is ascertained that no errors were made during sampling and/or con-
servation.
Σ Σ
anions = cations ≈ EC/100 (µS cm −1 ; for EC < 1500 µS cm −1 )
(11.2)
The unit mmol l−1 is useful to detect the stoichiometry of reactions; meq l−1 en-
ables checking the accuracy of analysis; water quality norms are usually given in
weight units like mg l−1 or ppm.

Recalculation of analytical units:

mmol l = mg l divided by gram formula weight

gram formula weight = weight in grams of 1 mol of atoms or molecules

1 mole = Avogadro’s number = 6*1023 atoms or molecules

meq l = mmol l * charge of ion

Alternatively, the EB & EC rule-of-thumbs can also be used to estimate the

concentrations of some major ions that are not easily measured with the available
field methods: Na++K+ and sulphate (SO42−). Hereto, it is assumed that your
analyses
K+ and SOwere2− done perfectly and the EB equals zero. You will estimate− Na −
++

− 4 in this way
2+ 2+
during the Dinkeldal fieldwork, as only EC, Cl , NO3 ,
HCO3 , Ca and Mg can be analysed with the field kit.

148
Figure 11.6: Equipment of the VU water laboratory to perform hydrochemical
analysis. Aquakem 200 discrete analyser (upper left), Radiometer Titralab TIM840
titration workstation (upper right), Dionex DX-120 IC equipped with IonPac AS14
column (lower left) and Varian 730-ES inductively coupled plasma-optical emis-
sion spectroscope (lower right).

149
Table 11.2: Concentrations (90th percentiles) of key water quality elements that are
typical for groundwater found in non-calcareaous aquifers under different land use
and land cover types in The Netherlands (Pers. comm. Igor Mendizabal). TH is the
total hardness, i.e. the sum of all calcium and magnesium compounds expressed as
calcium carbonate and usually given in mg l−1.
Land use category 90th percentile of water quality
NO3− SO42− Al3+ Ni TH As
µg l µg l µg l−1
−1 −1
mg l mg l−1 −1 −1 mmol l
Intensive agriculture 218 139 2065 51 4.5 7.5
Extensive agriculture 81 172 625 29 4.7 6.9
Intensive urbanization 89 161 124 20 5.1 11.9
Extensive urbanization 79 119 55 4 5.2 17.8
Nature 0 60 46 1 3.4 6.3
Forest 36 102 4008 72 2.5 4.5

11.6 Interpretation of hydrochemical regional data-sets

Now that you have your hydrochemical regional data-set, you want to extract the
information that it contains out of it. Some common research questions are:
• What different types of water are present?
• Which processes have caused the water compositions?
• What are the relations between the water types/chemistry and spatial infor-
mation such as land use/geology/soil type/geomorphology/hydrology?
Igor Mendizabal has created a classification system based on hydrochemi-
cal data of groundwater from hundreds of water supply pumping stations in The
Netherlands. An overview of his findings related to groundwater quality and land
use are presented in Table 11.2.
The following list presents some ideas for calculations and graphs you can
make to aid your interpretation:
a. Give a general description of the hydrochemical data-set:
a. Average, median, (5% and 95%) percentiles, and range of concentrations of
the various parameters (summarized in a Table via a spreadsheet). Do this
separately for each type of water (e.g. rainwater, seawater, and various types
of groundwater as determined via, for example, cluster analysis (see later)).
b. Compare concentrations to water quality norms (cf. Table 1.1 in Appelo and Postma
[2005]).
c. Dominant cat- and anions (HYFA analysis); or make Collins bar or pie di-
agrams like Figures 1.3 or 8.3 in Appelo and Postma [2005] for the group
means.

150
 d. What are the redox conditions, type of water (fresh, brackish, saline), pH?
e. Include a hydrogeological and geochemical (type of material: limestone,
clay, organic matter, gypsum, etc) description.

b. Calculate saturation indices (SIs; plus total inorganic carbon (TIC)) for se-
lected minerals using PHREEQC (via HYCA optionally) to find out which
minerals may have dissolved in the water. Use SOLUTION SPREAD and SE-
LECTED OUTPUT keywords (-saturation indices calcite, dolomite, gypsum,
etc (see database for more relevant minerals); check phreeqc practicals and/or
manual). Which mineral is the main buffer against soil acidification: calcite or
Al-hydroxides? Make cross-plot of their SIs.

c. Compare rainwater and groundwater samples to determine the extent of evapo-

transpiration that has occurred in the soil zone.

d. Compare samples to seawater ratios to find clues for processes like cation-
exchange, dissolution of minerals, sulphate-reduction, and pollution (acid rain,
fertilizer). See Appelo and Postma [2005] pages 29–30, 245–246.

a. GW chart (USGS) can be used to make a piper plot but you need to type all
data in the program (you cannot import a table).
b. GeoStiff (USGS) can be used to make Stiff diagrams that can subsequently
be imported in ArcView software. HYCA can also be used to make these
kinds of graphs.
e. Calculate correlation matrix to find out which parameters are correlated
+ +
and−
which are not. For example, components used in fertilizer (K , NH4 , NO3 ,
PO3−) may be correlated or Ca2+ and HCO− as a result of calcite dissolution.
4 3

f. Make cross-plots (xy plots in excel) to find and show relations between pa-
rameters (also calculate the coefficient of determination, r2). Showing seawater
mixing lines in these plots is often useful. For example, cations and sulphate
versus Cl−in coastal areas.

g. Compare time-series: to what extent are samples comparable over various years.
A student t-test (TTEST function in excel) can be done to determine whether
groups of samples are significantly different (in time or space).

h. Multivariate statistics analysis: principal component analysis (PCA), cluster

analysis, factor analysis (FA) to find out which samples are related and which
ones are different as well as the parameters that correlate. You can use the
free 30 days trial version of statistiXL (http://www.statistixl.com) to perform
all these multivariate statistics tests in excel.

i. Visualization of results in GIS: how do parameter values correlate with spatial

information such as geology, topography, and land-use?

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11.7 Hydrochemistry during MSc Hydrology fieldworks
11.7.1 Dinkeldal fieldwork, Twente, Netherlands
The learning goals are that you:

• Know how to take groundwater and surface water samples and to conserve
them.

• How (and why) to determine some parameters directly in the field and at the
field lab.

• How to check the accuracy of your analyses.

• How to make a chemical mass balance of a watershed via discharge and

chemical measurements. For example, a salt balance will be constructed
based on EC measurements of the streams.

• Know how to make a simple interpretation of a regional hydrochemical data-

set: relations to land use and major hydrochemical processes (like occur-
rence of calcite dissolution?).

11.7.2 Algarve fieldwork, Portugal

The learning goal is that you that you increase your skills in relating hydrochemical
information to hydrogeological processes in a regional perspective.

11.7.3 Aveiro fieldwork, Portugal

The learning goal is that you know how to make a strategy for a hydrological/hydrochemical
study and obtain water samples for hydrochemistry at optimal locations. In addi-
tion, you should know how to perform a (close to) complete interpretation of your
hydrochemical data-set (see Section 11.6).

152
The VU water level logger would produce the following line, where the first values
are date/time indicators and the last value is the water level deviation from a certain
level:
126 05 05 08 11 40 30 -00518
The data files can be imported into MS Excel or OpenOffice Calc, but can also be
processed and visualised by a Python script (see Chapter 13).
An exception is the Schlumberger – van Essen Diver water level logger, which
comes with its own software (Logger Data Manager) for setting-up, reading and
processing Diver data. The Logger Data Manager software facilitates correction
of the measured water level for atmospheric pressure changes and export of logger
data to ASCII text file or MS Excel file formats for further processing.

12.1 Using Python to process, analyse and visualise your

data
The basics of Python are taught in the Ecohydrology and Groundwater Flow Mod-
elling courses. Several Python scripts have been developed for the processing of
data (see also Chapter 13). These include the fitting of layers and resistances based
on EM-34 geophysical measurements (vertical electrical soundings) and the calcu-
lation of evaporation from meteorological data from the automatic weather station.
To use these scripts, please start Spyder, which is part of the Python(x,y) suite
of programs, or the more simple Idle Python interface. Then open the script and
take a look at the comments and instructions in the script that tell you how to use
it. In most cases you need to prepare an input data file and assign working and data
directories to tell Spyder/Python where your files are. The scripts are:
• stiff.py has been developped by Boris van Breukelen to allow you to make
stiff plots from hydrochemical data collected in Twente and Portugal field
courses.

• piper.py has also been developped by Boris van Breukelen to allow you to
make Piper plots from hydrochemical data collected in Twente and Portugal
field courses.

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 • em34.py was developped by Vincent Post and allows you to fit a model
of layers to EM-34 Vertical electrical soundings. An example script file
(em34 example.py) is also included

• meteoscript.py was developped by Maarten Waterloo and is used to pro-

cess data from the meteorological tower to obtain estimates of potential
and actual evaporation. It uses two function libraries (evaplib.py and me-
teolib.py) and needs a meteorological data input file. The meteolib.py library
contains meteorological functions to calculate actual and saturated vapour
pressures, constants such as λ, γ, cp, ρ, and the wind vector. The evap-
lib.py library contains functions for determining daily potential evaporation
rates with Penman [Penman, 1956], Priestley–Taylor [Priestley and Taylor,
1972], Makkink [Makkink, 1961] and FAO’s Penman Monteith ET0 refer-
ence evaporation for short, well-watered grass [Allen et al., 1998].

A Python manual for beginners, Python scripts and function libraries can be
downloaded from our web site at http://ecohydro.falw.vu.nl/python. Installation of
Python and other software is discussed in Chapter 13.

12.2 Spatial data processing and analysis

Spatial data is best processed with a Geographic Information System. Examples of
such systems are ARC/GIS from ESRI (http://www.esri.com) and the open source,
freely available GRASS software (http://grass.itc.it). Quantum GIS (QGIS) is an
alternative user-friendly open source GIS package licensed under the GNU General
Public License. QGIS is an official project of the Open Source Geospatial Founda-
tion (OSGeo). It runs on Linux, Mac OSX, and Windows and supports numerous
vector, raster, and database formats and functionalities.
Spatial data analysis has been the subject of the Basics in GIS (450226, 3
ECTS) and Applied GIS (450227, 3 ECTS) courses within the hydrology MSc
programme and will not discussed further. A field application of GIS is discussed
in Chapter ??. Note that working with time series is often difficult in GIS systems.

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